WO2000006631A1 - Method for producing a liquid additive on the basis of water-soluble, fine-grained polysaccharides, such as microbial or plant biopolymers and/or cellulose derivatives - Google Patents

Method for producing a liquid additive on the basis of water-soluble, fine-grained polysaccharides, such as microbial or plant biopolymers and/or cellulose derivatives Download PDF

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Publication number
WO2000006631A1
WO2000006631A1 PCT/IB1998/001158 IB9801158W WO0006631A1 WO 2000006631 A1 WO2000006631 A1 WO 2000006631A1 IB 9801158 W IB9801158 W IB 9801158W WO 0006631 A1 WO0006631 A1 WO 0006631A1
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characterized
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salzl
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Application number
PCT/IB1998/001158
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German (de)
French (fr)
Inventor
Manfred Akstinat
Willi Suter
Original Assignee
Holderbank Financiere Glarus Ag
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Priority to PCT/IB1998/001158 priority Critical patent/WO2000006631A1/en
Publication of WO2000006631A1 publication Critical patent/WO2000006631A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions or lattices by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions or lattices by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05Making solutions, dispersions or lattices by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/38Polysaccharides or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2301/00Characterised by the use of cellulose, modified cellulose or cellulose derivatives

Abstract

The invention relates to a method for producing a liquid additive on the basis of water-soluble, fine-grained polysaccharides, such as microbial or plant biopolymers and/or cellulose derivatives, according to which water-soluble polysaccharides, such as microbial or plant biopolymers and/or cellulose derivatives, in fine-grained dry powder form are dispersed in an aqueous solution of dissociable salts present at elevated concentration, notably a lyotropic salt solution.

Description

A process for the preparation of a liquid additive based on water-soluble, fine-grained Polvsacchariden such as microbial or plant Biopolvmeren and / or cellulose derivatives

The invention relates to a method for producing a liquid additive based on water-soluble polysaccharides, such as microbial or plant biopolymers and / or cellulose derivatives, in particular for the improvement of the processability and / or the rheological properties of binder suspensions.

Wasserlöslische polysaccharides such as ikrobielle biopolymers are proposed in connection with the improvement of the homogeneity of concrete preparations. Gums such as gum Arabicu, gellan gum (eg welan Gu) or generally glycans, such as starch derivatives, cellulose derivatives (such as. For example cellulose ether), dextrans, glucans, pectins, mannans, galactans, or heteropolysaccharides on based on arabinose, Galac- tose, glucuronic acid, mannose, rhamnose, or xylose are usually characterized by a high hydration rate and can therefore be a relatively high spontaneous and water ufnähme under construction a very high viscosity at concentrations already wt to first perform% , For the transport of such viscous hydro usually colloidal pseudo plastic properties can only be low-concentrated solutions in water. produce. It is thus becoming a very high water content transported, as the limiting concentration for well-pumpable aqueous hydrocolloids for binder suspensions generally about 2 to 3 wt.% Is.

The use of such water-soluble polysaccharides in aqueous binder systems is carried out primarily as a hydrocolloid loid, often together with superplasticizers as beispiels- as high molecular weight sulfonate derivatives. The strong rheological influence of aqueous binder suspensions by water-soluble polysaccharides requires to improve the processability at the same time relatively high amounts of further additives, in particular of Hochleistungsverflüssigern such as formaldehyde condensates of sulfonated naphthalene, sulfonated melamine or modify lignin sulfonates as well as their derivatives and / or mixtures of these or similar additives such as waste bindeverzögerer, reindeer accelerators, Schrumpfungskompensato-.

Due to the high and rapid water absorption fine-grained dry powder of the polysaccharides tend during uncontrolled mixing with water to form lumps and when added in small amounts and short mixing times to inhomogeneous distribution in aqueous systems.

In EP 505,096 Bl is a method by which such. B. welan gum can be prepared with increased hydration described.

The increased rate of hydration leads to the specifications of EP 505 096 Bl on the one hand, that such polysaccharides can be favorably mixed as solid with dry cement Namely, whereupon added only in the subsequent episode water. The production of storable homogeneous dry mixtures with fine-grained polysaccharides in solid material powders is not without problems and leads straight at high hydration to the fact that clumping can not be excluded. Difficulties in accurate dosage and uniform distribution of fast ydratisie- leaders polysaccharides are especially at low weight poly saccharide concentrations or -Zusatzmengen below 0.1.% To be expected, as may be usual in aqueous binder suspensions.

The invention now aims to establish a more advantageous and overall own direct additional form of wasserlöslischen polysaccharides with which it is possible without ensuring the risk of lumping a more accurate and reproducible dosing in the preparation of binder suspensions, while ensuring that the water-soluble polysaccharides are rapidly distributed homogeneously. To achieve this object, the inventive method essentially consists in that water-soluble polysaccharides are dis- pergiert as a fine-grained dry powder in an aqueous solution of dissociable salts of high concentration, in particular a lyotropic salt solution. thereby% alkali metal or alkaline earth salts of superplasticizers and / or water reducing agents are advantageously dissolved under vigorous stirring, with a minimum salt content by weight (depending on the nature of the ions) in the aqueous solution in an advantageous manner 20th weight. With this measure, the beneficial effect of the "Hofmeister lyotropic series" is exploited. Emissions for the production of such colloidal dispersants or suspensions of the polysaccharides are the "expectorant, ttel-withdrawing" properties of the ions of the dissociable salts and superplasticizer, for example the Na + - and Ca ++ - and the sulfonate to be used to approximate to block the entire "free water" by hydration of the ions. Simultaneously, the ions interact with the polar groups of the polysaccharides.

This to such a highly concentrated salt solutions added water-soluble polysaccharide itself can therefore no longer be solved, but only swelled and dispersed homogeneously. The expected formation of a highly viscous and non-pumpable gel with high polysaccharide no longer takes place. It is surprisingly even benign pumpable slightly-moving liquid, even at concentrations functions of the water-soluble polysaccharide of 5 to about 15 wt.% In H2O achieved. Such liquid preparation of water-soluble polysaccharides in highly concentrated salt solutions has several technological advantages: Water-soluble polysaccharides can be dosed much more advantageous in the sequence and homogeneous split binder suspensions. That at the same time introduced in this solution for ion of super condensers oa concrete admixtures allow the preparation also highly concentrated polysaccharide dispersions, with the result that the carrying weight of the dispersions, and hence the transport costs and the cost of storage tanks and stocking can be considerably reduced ,

The manufacturing method according to the invention is advantageously carried out so that dilute aqueous solutions of commercially available superplasticizer and / or water reducing agent and / or other concrete admixtures are concentrated by further addition of solid salts or superplasticizers with stirring and in that during the stirring defoaming agent in the solution of salts or superplasticizers are introduced. This will in such solutions further greatly reduced or made disappear by ion-hydration all to encrypt the content of the "free water".

Advantageously, it is this procedure is such that the aqueous salt solution from complex mixtures dissociable salts of setting regulating and / or condensers and / or water reduction mittein and / or additional Schrumpfungskompensatoren, wherein, preferably, the lyotropic salt solution of the dissociable alkali and / or alkaline earth metal salts and / or ammonium salts and / - or salts of organic basic oxygen and / or nitrogen is compounds. Preferably, the comparison here can of liquid and water reducing agent selected from salts of formaldehyde condensates of melamine sulphonates and / or naphthalene sulfonates and / or lignin sulphonates and / or acrylic and / or maleic anhydride copolymers are made.

A particularly advantageous, liquid preparation can be achieved by the fact that fine-grain, water-soluble polysaccharide powder wt directly in amounts of 1 to 15%, preferably 5 to 10 wt.%, Are stirred into a concentrated salt solution of superplasticizers oa concrete admixtures. The grain size of the water-soluble polysaccharide powder should be in the range of 5 to 100 microns as possible to optimum stability of the

Polymer dispersion to be achieved. Such water-soluble polysaccharide powder can be dispersed in relatively high concentrations in water thus, the required for the desired rheological properties of binder suspensions amounts of superfluidifiers and / or other additives thus already advantageously can be incorporated with the same additive in a concrete or mortar. Advantageously, this is so proceeded that the aqueous lyotropic salt solutions are brought from Superverflüssigersalzen by further addition of solid Superverflüssigersalzen with stirring to a concentration close to its saturation concentration.

Total polysaccharide condenser mixtures result in a substantial technological improvement in the processability and the rheological properties of Bindemit- telsuspensionen. Problems, as would occur with a lack of synchronization between the prehydration of water-soluble polysaccharides and the binders can be avoided by the inventive formulation.

It is particularly advantageous for the novel process is the use of defoamers. Using these products can virtually eliminate the adhering a polymer powder air bubbles and condensers homogeneous to another, highly concentrated non-foaming solutions of super- and / or other concrete admixtures with water-soluble polysaccharides, in particular biopolymers and / on the one hand in the preparation of aqueous suspensions of water-soluble polysaccharides or cellulose derivatives, are prepared by stirring.

A typical preparation of the liquid additive according to the invention is advantageously carried out such that with fine-grained biopolymer or cellulose derivative powders offset highly con- centrated salt solution of at least 15 min, preferably about 30 minutes, after the addition of the last subset of biopolymers and / or cellulose derivatives further stirred is and the resulting foam after the end of the stirring, with an additional amount of less than 0.5 wt.% defoaming agent is destroyed, whereby ultimately a stable, homogeneous, highly concentrated poly sacchariddispersion can be achieved.

In a particularly advantageous manner is such as to proceed such that first condensers an aqueous salt solution of commercially available super and / or other additives such. B. setting regulating and / or Schrumpfkompensatoren by weight on a salt content of 20 to 60.%, Preferably 40 to 45 wt.%, By weight with the addition of 0.01 to 0.5.% Defoamer is accommodated. Thereafter% water-soluble polysaccharide powders are preferably from 5 to 8. Given in the aqueous salt solution, preferably wherein the salt solution for 15 min is stirred, and the further incremental addition of water-soluble polysaccharide powder is carried out under at least 30 minutes of stirring. After the suspension of the

Dispersion of at least another 30 min, preferably about 60 min, are added yet conclusively 0.01 to 0.5.% Defoamer

(Based on the weight of the solution) was stirred.

In summary, by way of example proposed for the production of a typical plasticiser to improve the homogeneity of binder suspensions here fine-grained biopolymer and / or cellulose derivative powder into an aqueous highly concentrated salt solution of dissociable condensers on the basis of formaldehyde condensates of melamine sulfonate and / or naphthalene and / introducing or lignin sulfonates and / or acrylic and / or maleic anhydride copolymers, with stirring, with a minimum content of all dissociable Verflüssigerkomponenten in the aqueous solution of 20 wt.% is. Fine-grained biopolymer or cellulose derivative powder may be present in amounts of 1 to 15% are stirred flüssigern in such solutions of Superver-, whereby a stable, yet easily movable and verpumpbare suspension.

The liquid additive of the invention are preferably for binder suspensions based on cement (concrete, mortar), gypsum and / or other hydraulic binders in water, possibly with aggregates or additives, wherein the resulting liquid additive for the improvement in workability and the rheological properties of binder suspensions is used.

Claims

Patentanspr├╝che:
1. A method for producing a flüssigen additive based on wasserlöslichen polysaccharides, such as micro- or vegetable biellen biopolymers and / or cellulose derivatives, in particular für improving the processability and / or the rheological properties of binder suspensions, characterized in that daß wasserlösliche polysaccharides, such as microbial or plant biopolymers and / or cellulose derivatives such as feinkörnige dry powder in a wäßrigen Lösung dissociable salts of high concentration, in particular a lyotropic Salzlösung be dispersed.
2. The method according to claim 1, characterized in that the highly concentrated daß wäßrige Salzlösung from dissociable
Ammonium and / or alkali and / or alkaline earth salts of Abbinderregulatoren and / or Superverfl├╝ssigern and / or water reducing agents is.
3. The method of claim 1 or 2, characterized in that the minimum amount of weight daß dissociable and especially lyotropic salts in the polymer dispersion 20th beträgt%.
4. The method of claim 1, 2 or 3, characterized in that the daß Korngröße the wasserlöslichen polysaccharide powder
Range from 5 to 100 ╬╝m located.
5. A method according to one of the Ansprüche 1 to 4, characterized in that the wäßrige Salzlösung daß from complex mixtures dissociable salts of setting regulating and / or Verflüssigern and / or water reducing agents and / or zusätzlichen Schrumpfungskompensatoren exists.
6. The method according to one of Ansprüche 1 to 5, characterized characterized marked, daß lyotropic Salzlösung from dissociable
Alkali and / or alkaline earth metal salts and / or ammonium salts and / - or salts of organic bas ischer Oxygen f - and / or f Stickstof compounds.
7th AV Ahren according to one of Ansprüche 1 to 6, characterized denotes Ge, daß the AV lüssiger and water reducing agent selected from salts of formaldehyde condensates of the Melaminsulf onate and / - or naphthal insul f onate and / or Ligninsul f onths and / or acrylic and / or Maleinsäureanhydrid copolymers exist.
8th . The method according to Ansprüche 1 to 7, characterized in that the daß wäßrigen lyotropic Salzlösungen from Superver- flüss igersal zen by further addition of f th Superver- it flü ss igersal zen be brought under Rühren to a concentration near its Sättigungskonzentration.
9. The method according to one of Ansprüche 1 to 8, characterized in that daß Entschäumungsmittel in the lyotropic Salzlösung from Superverflüssigern and / or other additives are introduced.
10. The method according to one of Ansprüche 1 to 9, characterized in that daß feinkörnige, wasserlösliche polysaccharides, such as microbial or plant biopolymers and / or cellulose derivative powder in amounts of from 1 to 15 weight .%, preference, from 5 to 10 wt.%, flüssigern in a lyotropic Salzlösung from Superver- and / or other additives are eingerührt.
11. The method according to one of Anspr├╝che 1 to 10, characterized da├ƒ, the saccharides with feink├╢rnigen wasserl├╢slichen poly-, such as microbial or plant biopolymers and / or cellulose derivative powder offset lyotropic Salzl├ ╢sung least 15 min, preferably about 30 min after the addition of the last aliquot of the polysaccharides, such as micro- or vegetable Bieller biopolymers and / or cellulose derivatives powder, is weiterger├╝hrt and after the end of R├ ╝hrens resulting foam with an amount of less than 0.5 wt.% Entsch├ñumer is zerst├╢rt.
12. The method according to one of Ansprüche 1 to 11, characterized in that first a daß wäßrige Salzlösung from handelsüblichen Superverflüssigern and / or other additives such. is as setting regulating and / or Schrumpfkompensatoren by weight on a salt content of 20 to 60.%, preferably 40 to 45 wt.%, by weight with the addition of 0.01 to 0.5.% Entschäumer accommodated.
13. The method according to one of Ansprüche 1 to 12, characterized in that daß 0.01 to 0.5 wt.% Entschäumer in a lyotropic Salzlösung eingerührt be before feinkö rnige, wasserlösliche polysaccharides, such as microbial or plant biopolymers and / or cellulose derivative powder may be added.
14. The method according to one of Ansprüche 1 to 13, characterized in that the lyotropic daß Salzlösung the Superverflüssiger and / or other additives for at least 15 min and is gerührt daß the subsequent addition of feinkörnigen, wasserlöslichen polysaccharides, such as microbial or plant biopolymers and / or cellulose derivative powders is carried out under at least 30 minütigem Rühren and daß for a suspension of the Lö solution über at least another 30 min, in particular about 60 min, 0.01 to 0.5 wt.% Entschäumer be added.
15. The method according to one of Ansprüche 1 to 14, characterized in that the daß binder suspensions based on cement (concrete, Mörtel), gypsum and / or other hydraulic binders in water, optionally with additives or are built additives.
PCT/IB1998/001158 1998-07-29 1998-07-29 Method for producing a liquid additive on the basis of water-soluble, fine-grained polysaccharides, such as microbial or plant biopolymers and/or cellulose derivatives WO2000006631A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/IB1998/001158 WO2000006631A1 (en) 1998-07-29 1998-07-29 Method for producing a liquid additive on the basis of water-soluble, fine-grained polysaccharides, such as microbial or plant biopolymers and/or cellulose derivatives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU83527/98A AU8352798A (en) 1998-07-29 1998-07-29 Method for producing a liquid additive on the basis of water-soluble, fine-grained polysaccharides, such as microbial or plant biopolymers and/or cellulose derivatives
PCT/IB1998/001158 WO2000006631A1 (en) 1998-07-29 1998-07-29 Method for producing a liquid additive on the basis of water-soluble, fine-grained polysaccharides, such as microbial or plant biopolymers and/or cellulose derivatives

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2695866A3 (en) * 2013-05-24 2017-07-05 Basf Se Modified rheology additive

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482533A2 (en) * 1990-10-22 1992-04-29 Aqualon Company Sodium formate fluidized polymer suspensions
EP0505096A2 (en) * 1991-03-20 1992-09-23 Monsanto Company Rapidly hydrating welan gum
EP0507419A1 (en) * 1987-05-07 1992-10-07 Monsanto Company Low viscosity welan gum and process for preparation thereof
EP0619340A2 (en) * 1993-04-08 1994-10-12 Aqualon Company Thermally stable thiosulfate hydroxyethylcellulose suspension
WO1996018676A1 (en) * 1994-12-15 1996-06-20 Akzo Nobel N.V. Method for producing a suspension in water of a cellulose ether, and dry mixture suitable for use in the production of the suspension
WO1996040598A1 (en) * 1995-06-07 1996-12-19 The Nutrasweet Company Stable suspension of hydrocolloids and superplasticizer
WO1997022564A1 (en) * 1995-12-15 1997-06-26 Monsanto Company Methods for improved rheological control in cementitious systems

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0507419A1 (en) * 1987-05-07 1992-10-07 Monsanto Company Low viscosity welan gum and process for preparation thereof
EP0482533A2 (en) * 1990-10-22 1992-04-29 Aqualon Company Sodium formate fluidized polymer suspensions
EP0505096A2 (en) * 1991-03-20 1992-09-23 Monsanto Company Rapidly hydrating welan gum
EP0619340A2 (en) * 1993-04-08 1994-10-12 Aqualon Company Thermally stable thiosulfate hydroxyethylcellulose suspension
WO1996018676A1 (en) * 1994-12-15 1996-06-20 Akzo Nobel N.V. Method for producing a suspension in water of a cellulose ether, and dry mixture suitable for use in the production of the suspension
WO1996040598A1 (en) * 1995-06-07 1996-12-19 The Nutrasweet Company Stable suspension of hydrocolloids and superplasticizer
WO1997022564A1 (en) * 1995-12-15 1997-06-26 Monsanto Company Methods for improved rheological control in cementitious systems

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2695866A3 (en) * 2013-05-24 2017-07-05 Basf Se Modified rheology additive

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